Compounds useful as chemical precursors in chemical vapor deposition of silicon-based ceramic materials

ABSTRACT

In order to reduce the rate of coke formation during the industrial pyrolysis of hydrocarbons, the interior surface of a reactor is coated with a thin layer of a ceramic material, the layer being deposited by thermal decomposition of a non-oxygen containing silicon-nitrogen precursor in the vapor phase, tin an inert or reducing gas atmosphere in order to minimize the formation of oxide ceramics.

This is a Division of application Ser. No. 08/155,769 filed on Nov. 23,1993, now U.S. Pat. No. 5,413,813.

RELATED APPLICATION

This application is related to U.S. patent application Ser. No.07/783,264, now U.S. Pat. No. 5,208,069 which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the thermal decomposition of compoundsin contact with a metal or metal oxide surface to form a ceramic coatingon the surface. In particular, the ceramic coating may be formed on aheat-resistance alloy steel or alloy steel oxide reactor for use inchemical processes. The present invention provides an improved chemicalreactor processing environment for pyrolysis processes such as crackingor the disproportionation of hydrocarbons.

2. Discussion of the Background

Coking is a significant problem in high-temperature chemical reactions,such as the pyrolysis of hydrocarbons, particularly in the production ofethylene.

Ethylene, the lightest olefinic hydrocarbon, is the most importantbuilding block of the petrochemical industry. Ethylene is producedalmost exclusively via the pyrolysis of hydrocarbons in tubular reactorcoils which are externally heated by a furnace (see: Chapter 8 inPyrolysis of Hydrocarbons, p.109-142, Marcel Dekker Inc., New York(1980)). High selectivity toward the production of desired olefins(i.e., ethylene and propylene) and diolefins (i.e., butadiene) withminimum methane and hydrogen production and coking in the coils leadingto longer heater runs are desired. This is achieved by operating thepyrolysis heaters at high temperatures (750°-900° C.), short residencetimes (0.1-0.6 sec.) and low hydrocarbon partial pressures. Steam isadded to the feedstock to reduce the hydrocarbon partial pressure andthe amount of carbon deposited on the tube walls.

Steamless cracking has been investigated as a potential means ofincreasing production capacity and maximizing energy efficiencies (see"Steamless Pyrolysis of Ethane to Ethylene", Paper 101, presented at ameeting of the American Chemical Society, Boston, Mass., April 1990, byY. Song, A. A. Leff, W. R. Kliewer and J. E. Metcalf). The work citedabove was performed in a tube made entirely of silicon carbide. The useof tubes constructed of silicon carbide, however, would not be possibleon an industrial scale because of the low mechanical reliability andfabrication problems of this material.

Tubular reactor coils, also known as pyrolysis heaters, are an importantfacet of operation to consider partly because of coke deposition (see:Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 9, "Ethylene" J.Wiley & Sons Inc., New York , (1979)). The mechanism of coke formationhas been postulated (see L. F. Albright & J. C. Marck, Ind. Eng. Chem.Res., vol 27, 731 and 743 (1988)), but has yet to be modeled in preciseterms.

The reduction of the coking rate and the extension of the reactor runtime have been the subject of several investigations and commercialapplications (see for example the Products Bulletins G-262, G-5263,G-5267, G-5268 by Nalco Chem. Co., Petroleum and Process ChemicalDivision, 1800 Eperson Bldn.--Houston, Tex.).

For instance, the use of a silicon dioxide layer to inhibit cokeformation inside thermal cracking reactors is known from UK-1,332,569and U.S. Pat. No. 4,099,990. In particular, in U.S. Pat. No. 4,099,990,the silicon dioxide coating is obtained by thermal decomposition of analkoxysilane in the vapor phase. The silicon dioxide coating reducescoking rates. Although any non-catalytic surface would be effective forcoke reduction the factors which determine industrial applicability of acoating material are the following: the thermal expansion match of thelayer with the metal, the melting point of the coating material, thedegree of strength, brittleness, adherence, the resistance to wear andcorrosion, and so on. From this point of view, silicon dioxide filmssuffer from many drawbacks, mainly due to the wide gap between thethermal expansion coefficients of silicon dioxide and of the metalsubstrate. This mismatch causes poor adhesion of the layer to thesubstrate, poor thermal shock and spallation resistance.

U.S. Pat. No. 3,536,776 discloses a method of reducing coke in the hightemperature conversion of hydrocarbons by utilizing a reactor which iscoated with a metal ceramic material containing particles of acatalytically inert, refractory solid ceramic substance dispersed inchromium.

U.S. Pat. No. 5,208,069 discloses a method for passivating the innersurface of hydrocarbon pyrolysis tubes by deposition of a ceramiccoating. Specific silicon-containing compounds are disclosed asprecursors in the ceramic deposition process.

There remains a need for an apparatus which exhibits a reduced tendencyto undergo coking. In particular, there remains a need for a method andan apparatus for pyrolyzing hydrocarbons which are free of theabove-described drawbacks. There also remains a need for a method forproducing such an apparatus.

SUMMARY OF THE INVENTION

Accordingly, it is an object of the present invention to provide a novelapparatus which exhibits a reduced tendency to undergo coking.

It is another object of the present invention to provide a novelapparatus for the pyrolysis of hydrocarbons which minimizes the cokingrate.

It is another object of the present invention to provide a method forpreparing such an apparatus.

It is another object of the present invention to provide a method ofpyrolyzing hydrocarbons utilizing such an apparatus.

These and other objects, which will become apparent during the followingdetailed description, have been achieved by the discovery that thereduction of the coking rate in reactors which are subject to coking canbe achieved by the controlled deposition, on the inner surface of thereactor, preferably a tubular reactor, of a coating derived from aprecursor compound containing at least two silicon atoms bonded to anitrogen atom, in an inert or reducing gas atmosphere in order to limitthe formation of oxide ceramics.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Accordingly, the present invention relates to a method for treating theinner surface of a reactor which is subject to coking, wherein thesurface is coated with a thin layer of a ceramic material, the layerbeing deposited by thermal decomposition of a silicon-nitrogen precursorin the vapor phase, in a controlled inert or reducing gas atmosphere inorder to minimize the formation of oxide ceramics.

The thus-obtained ceramic material consists essentially of siliconcarbide, silicon nitride, silicon carbonitride or mixtures thereof.Minor amounts of silicon dioxide, silicon oxycarbide or siliconoxynitride may form during the deposition without impairing theeffectiveness of the layer. Thus, the mole fraction of oxygenincorporated in the ceramic layer is suitably 0 to 20 mol. %, preferably0 to 10 mol. %. Moreover, free carbon may be present in the ceramiccomposition, derived from "excess" carbon based on stoichiometryconsiderations. The amount of free carbon is suitably 0 to 30 mol. %,preferably 0 to 20 mol. %. Additionally, up to 10 mol. % of other inertmaterials derived from the precursors or the gas carrier may beincorporated in the coating without detrimental effects.

The principal advantage deriving from Chemical Vapor Deposition (CVD) ofthin films (see Vapor Deposition, Eds. C. F. Powell, J. H. Oxley, J. M.Blocher Jr., J. Wiley & Sons, N.Y. (1966)), is the atom-by-atom natureof the deposition process which eliminates outgassing problems. Thisprocess results in high film quality.

The choice of CVD precursor compounds that are likely to serve asefficient CVD precursors is dependent on a variety of factors. Thechoice of the precursor must take into account such factors as thephysical properties, ease of synthesis and handling, and the conditionsrequired for thermolysis of the precursor in order to make coatings ofsuitable quality.

CVD precursors suitable for the present invention are selected fromsilicon-nitrogen compounds which are volatile at temperatures below thedeposition process. These compounds will contain two or more siliconatoms with the other atoms being carbon, nitrogen, or hydrogen. Thesecompounds may also contain other elements, such as chlorine. Theflexibility in kinetics and decomposition mechanisms of siliconcompounds affords deposition control on the reactor surface.

In the method of the present invention, the precursor compound is acompound containing nitrogen, carbon and hydrogen atoms and at least twosilicon atoms, where at least two silicon atoms are bonded to a singlenitrogen atom (Si-N-Si). However, the precursors of the presentinvention are not limited to compounds containing only two silicon atomsand may contain a plurality of silicon atoms bonded to nitrogen atoms.Generally, the precursor compounds will contain from 2 to about 8silicon atoms. The precursors may be cyclic or acyclic and willgenerally contain up to about 30 carbon atoms, preferably 1-20 carbonatoms. When only 2 or 3 silicon atoms are present in the precursor andthese 2 or 3 silicon atoms are bonded to the same nitrogen atom, atleast one of the silicon atoms must contain at least one alkyl grouphaving at least 2 and up to 20, preferably 1-8 carbon atoms. Thecompound nonamethyltrisilazane is also within the scope of the presentinvention, even though this compound contains 3 silicon atoms bonded toa single nitrogen atom and the silicon atoms are methyl substituted.

In one embodiment (A) of the present invention, the precursor has thestructure shown below ##STR1## wherein each R is hydrogen, C₁₋₂₀ alkyl,halogen (preferably chlorine) or NR₁ R₂ where R₁ and R₂ are hydrogen,C₁₋₈ alkyl or SiR₃ R₄ R₅ and R₃, R₄ and R₅ are hydrogen, C₁₋₂₀ alkyl,halogen (preferably chlorine) or NR₁ R₂. The group X is hydrogen,lithium or SiR₃ R₄ R₅ where R₃, R₄ and R₅ are as defined above.Precursor compounds within this embodiment of the invention must have 2silicon atoms bonded to a nitrogen atom. For compounds in thisembodiment containing only 2 or 3 silicon atoms bonded to the samenitrogen atom, at least one group R must be an alkyl group containing atleast 2 and up to 20, preferably 1-8 carbon atoms.

Preferred compounds within this embodiment of the invention arecompounds in which R is C₁₋₈ alkyl, more preferably C₁₋₄ alkyl, evenmore preferably methyl. Among these preferred embodiments, substituent Xis preferably SiR₃ R₄ R₅ where R₃, R₄ and R₅ are as defined above.

Specific compounds within the first embodiment include N-Li-hexamethyldisilazane, heptamethyl-chloro-trisilazane,1,3-dichloro-1,1,3,3-tetramethyl disilazane, 1,2,3-trichloro hexamethyltrisilazane, ethyl-heptamethyl trisilazane, chloro-octamethyltrisilazane, nonamethyl trisilazane, N-lithio-1,3-dichloro-tetramethyldisilazane, 1,2,3-trichloro hexamethyl trisilazane, and1,1-dichloro-1-ethyl-trimethyl disilazane.

In a second embodiment (B) of the invention, the precursor compound iscyclic and has the structure shown below ##STR2## where R₆ is hydrogenor C₁₋₂₀ alkyl; and R₇ is hydrogen, C₁₋₂₀ alkyl (preferably C₁₋₈ alkyl),lithium or SiR₈ R₉ ₁₀ where R₈, R₉ and R₁₀ are, independently, hydrogenor C₁₋₂₀ alkyl, preferably C₁₋₈ alkyl, more preferably methyl.Particularly preferred compounds within this embodiment of the inventionare cyclic precursors in which R₆ is methyl and each R₇, independently,is hydrogen or SiR₈ R₉ R₁₀, where R₈, R₉ and R₁₀ are hydrogen or methyl.

Specific examples of compounds within the second embodiment includeN-dimethylsilyl-1,1,3,3,5,5-hexamethylcyclotrisilazane;bis(N-dimethylsilyl)-1,1,3,3,5,5-hexamethylcyclotrisilazane;tris(N-dimethylsilyl)-1,1,3,3,5,5-hexamethylcyclotrisilazane;1,1,3,3,5,5-hexamethyltrisilazane andN-lithio-1,1,3,3,5,5-hexamethylcyclotrisilazane.

In a third embodiment (C) of the present invention, the precursorcompounds have the structure shown below ##STR3## wherein R₆ and R₇ areas defined above and R₁₁ is hydrogen or C₁₋₂₀ alkyl, preferably C₁₋₈alkyl, more preferably methyl. In the compounds of this embodiment, afourth silicon atom forms bonds to 2 nitrogen atoms in the 6-memberedring thereby forming a bicyclic ring system. In a fourth embodiment (D)of the invention, the precursor compounds have the cyclic structureshown below ##STR4## wherein R₆ is as defined above and R₁₂ is hydrogenor C₁₋₂₀ alkyl, preferably C₁₋₈ alkyl, more preferably methyl.

In a fifth embodiment (E) of this invention, the precursor compound hasthe structure shown below ##STR5## wherein R is hydrogen, C₁₋₂₀ alkyl,halogen (preferably chlorine), NR₁ R₂ (where R₁ and R₂ are,independently, hydrogen, C₁₋₂₀ alkyl, halogen (preferably chlorine) orSiR₃ R₄ R₅ where R₃, R₄ and R₅ are hydrogen, C₁₋₂₀ alkyl or NR₁ R₂); andA is a divalent alkylene, arylene or alkylarylene group. Preferably, Ais a straight-chain or branched C₂₋₆ alkylene, a C₆₋₁₀ arylene group ora C₇₋₁₆ alkylarylene group. By "alkylarylene" is meant a group havingthe formula --(CH₂)_(n) --Ar--(CH₂)_(m) ---, where Ar is a C₆₋₁₀ arylgroup such as phenyl or naphthyl, and n and m are integers such that thesum of n and m has a value in the range 1-10. In compounds within thisembodiment of the invention, 1, 2 or 3 of the R groups on each siliconatom bonded to A is NR₁ R₂ and at least one of R₁ and R₂ is SiR₃ R₄ R₅.Particularly preferred are compounds in which R₁ and R₂ are both SiR₃ R₄R₅ and R₃, R₄ and R₅ are methyl.

An additional embodiment (F) for use in the invention has the structureshown below. ##STR6##

Mixtures of different precursor compounds may also be suitably used. Theprecursor compounds used in the present invention may contain impuritiesin minor amounts such that the overall properties of the depositedceramic are not altered. For example, when the precursor is preparedfrom a lithium-containing compound, minor amounts of lithium-containingcompounds may be present in the precursor without affecting the overallproperties of the deposited ceramic.

The method of coating according to the present invention is carried outby simply heating one or more precursor compounds in a controlled inertor reducing gas atmosphere, i.e., under conditions which minimize theformation of oxide ceramics, thereby obtaining certain advantages inthat the stoichiometry of the ceramics is controllable. It is possiblethat the ceramics' physical properties (i.e., thermal expansion andstrength) can be influenced.

For this purpose, carrier gases which are inert or reducing under thereaction conditions, such as nitrogen, argon, helium, methane, ethylene,ethane, hydrogen and mixtures thereof are suitable. Minor amounts ofoxygen or oxygen-containing gases, such as carbon dioxide and monoxide,do not impair the properties of the obtained coating.

The concentration of the precursor in the carrier gas must be adjustedso as to avoid the formation of powders. The optimum concentration thusdepends on the identity of the precursor and on the operativeconditions. In general the concentration is suitably less than 10.0%v/v, preferably less than 5.0% v/v.

The deposition is generally carried out at atmospheric or slightlysubatmospheric pressure.

Because the decomposition kinetics are different for differentprecursors, the temperature of deposition can vary from about 600°to900° C., preferably about 700°to 800° C. Decomposition kinetics aredirectly responsible for the deposition behavior observed. It isimportant to note that limitations to deposition temperature are mainlyimposed by engineering technical reasons: for example, the uppertemperature limit for precursor deposition is determined by the uppertemperature limit of the furnace. The freedom to choose among precursorspossessing different decomposition characteristics affords theopportunity to accommodate the limitations of the apparatus. Throughadjusting flow rate of carrier gas, it is possible to control themovement of the maximum deposition zone over the reactor length fromreactor inlet to reactor outlet.

The desired thickness of the ceramic coating should be such to providecomplete or near coverage of the reactor inside surface. The thicknessrequired for having an effective coating depends on the surface of thereactor. The local thickness can be affected by surface roughness.Typically, coatings of 1 to 20 μm are used.

Thus, the present invention is characterized by the following advantagesand features:

(1) The ceramic coating retards the formation of coke deposits by thepassivation of the catalytically active metal surfaces which are presentin reactor coils in steam or steamless hydrocarbon pyrolysis reactors. Afirst consequence is an increase in productivity of ethylene, since thereduction in coking rate increases the duration between decoking cycles.

(2) Significant operation cost savings are realized since the decreasein the rate of coke formation also decreases the amount of energyrequired in the form of heat and therefore less fuel is consumed.

(3) The presence of the ceramic layer may upgrade the carburizationresistance of steam cracker alloy tubing, resulting in a cost savingsfrom less frequent tube replacements.

(4) With respect to the known methods where silicon dioxide is used, asignificant improvement in the match of thermal expansion coefficientsbetween the ceramic coating presented herein and the alloy steel reactorproduces an increase in the operative life of the coating itself.

(5) Another advantage of in-situ precursor chemical vapor deposition isthat more coating can be applied if and when coating failure occurs.

It is to be understood that, although the present method is particularlywell suited for the coating of apparatus used in the pyrolysis ofhydrocarbons, particularly in the production of ethylene, the presentmethod may be beneficially applied to any apparatus which is subject tocoking.

The present invention also relates to apparatuses which are subject tocoking. In a preferred embodiment, the apparatus possesses at least onereactor tube of which a surface is coated with a layer of a ceramicmaterial consisting essentially of silicon carbide, silicon nitride,silicon carbonitride or mixtures thereof. Minor amounts of silicondioxide, silicon oxycarbide or silicon oxynitride may form during thedeposition without impairing the effectiveness of the layer. Thus, themole fraction of oxygen incorporated in the ceramic layer is suitably 0to 20 mol % preferably 0 to 10 mol. %. The amount of free carbon issuitably 0 to 30 mol. %, preferably 0 to 20 mol. %.

A general discussion of apparatuses used for the pyrolysis ofhydrocarbons is given in Kirk-Othmer Encyclopedia of ChemicalTechnology, vol. 9, "Ethylene", pp 393-431, Wiley N.Y. (1980), which isincorporated herein by reference. A discussion of the apparatus andreaction condition parameters to be considered when maximizing theproduction of ethylene in hydrocarbon pyrolysis is provided in L.E.Chambers et al, Hydrocarbon Processing, January 1974, pp. 121-126, whichis also incorporated herein by reference.

It is preferred that the present apparatus be for the pyrolysis ofhydrocarbons. It is particularly preferred that the present apparatus befor the steam or steamless production of ethylene by cracking.

The present invention also relates to a method of pyrolyzing ahydrocarbon by utilizing a reactor in which the inner surface is coatedwith a layer of a ceramic material consisting essentially of siliconcarbide, silicon nitride, silicon carbonitride or mixtures thereof.Minor amounts of silicon dioxide, silicon oxycarbide or siliconoxynitride may form during the deposition without impairing theeffectiveness of the layer. Thus, the mole fraction of oxygenincorporated in the ceramic layer is suitably 0 to 20 mol. %, preferably0 to 10 mol. %. The amount of free carbon is suitably 0 to 30 mol. %,preferably 0 to 20 mol. %.

As noted above, a general discussion of the pyrolysis of hydrocarbon isprovided in Kirk-Othmer Encyclopedia of Chemical Technology, vol. 9, pp.393-431, Wiley, N.Y. (1980). Thus, the present method of pyrolysis mayutilize a variety of feedstocks such as ethane, propane, ormulticomponent hydrocarbon feedstocks (e.g., natural gas liquids,naphthas, and gas oils). The particular conditions utilized, such astemperature, pressure, residence time, flow rate, etc., will depend onthe particular geometry and characteristics of the reactor and identityof the feedstock being used. Selection of the appropriate reactionconditions is within the abilities of one having ordinary skill in thisart. Preferably, the present method for pyrolyzing hydrocarbons iseither the steam or steamless production of ethylene.

The precursor compounds of the present invention are prepared byreactions using commonly available starting materials such as hexamethyldisilazane (HMDS) and hexamethyl cyclotrisilazane (HMCTS) which arecommercially available. HDMS has the structure shown below.

    Si(CH.sub.3).sub.3 --NH--Si(CH.sub.3).sub.3

HMDS and corresponding disilazanes can be readily N-lithiated byreaction with an organolithium reagent such as n-butyllithium in dryinert solvents such as hydrocarbons and ethers. The N-lithio-disilazaneis then reacted with a chlorosilane to produce compounds having 3silicon atoms bonded to a single nitrogen atom. Suitable chlorosilaneshave the structure Cl-SiR₃ R₄ R₅ where R₃, R₄ and R₅ are hydrogen,halogen or C₁₋₂₀ alkyl. The chlorosilane may contain 1, 2 or 3 chlorineatoms. Suitable chlorosilanes include ethyl dichlorosilane ,diethyldichlorosilane, methyldichlorosilane, dimethylchlorosilane, etc.When the chlorosilane contains 2 or 3 chlorine atoms, the productobtained by reacting the N-lithio-disilazane with the chlorosilane willcontain unreacted Cl-Si bonds which can be further reacted withN-lithiated disilazane to increase the number of silicon atoms in theprecursor. N-lithio-disilazane and other compounds containing a Cl-Sibond can also be reacted with Grignard reagents having the structureR-MgBr where R is C₁₋₂₀ alkyl, preferably C₂₋₂₀ alkyl, more preferablyC₂₋₈ alkyl to introduce alkyl groups having two or more carbon atomsinto the product. Alternatively, compounds containing a Cl-Si bond maybe reacted with an organolithium reagent having the formula R-Li where Ris C₁₋₂₀ alkyl, preferably C₂₋₂₀ alkyl, more preferably C₂₋₈ alkyl.

Similarly, the cyclic precursors of the present invention are preparedby first lithiating cyclotrisilazanes such as HMCTS with anorganolithium reagent in a dry inert solvent. The N-lithiatedcyclotrisilazane is then reacted with a chlorosilane in the same manneras described above. Bicyclic precursors are formed by reacting abis(N-lithio)cyclotrisilazane with a chlorosilane or chlorosilazanehaving two chlorine atoms. For example, N-dimethylsilylcyclotrisilazanecan be reacted with two equivalents of n-butyllithium to formbis(N-lithio)-N-dimethylsilyltrichlorosilazane. The bis(N-lithio)compound can then be reacted with methyl dichlorosilane to form aprecursor of embodiment (C) where each R₆ is methyl, one R₁₁ is hydrogenand the other R₁₁ is methyl and R₇ is dimethylsilyl. Similarly,tris(N-lithio)cyclotrisilazanes are reacted with chlorosilanes havingthree chlorine atoms to form the cyclic compounds of embodiment (D). Inan analogous reaction, tris(N-lithio)-HMCTS is reacted with1,2,3-trichlorohexamethyltrisilazane to form the compound of embodiment(F).

In a similar manner, the compounds of embodiment (E) are prepared byreacting a chlorosilane with a divalent Grignard reagent or divalentorganolithium reagent having the structure BrMg-A-MgBr or Li-A-Li. Thesedivalent organometallic reagents are prepared by conventional methods,i.e. reacting the corresponding dihalo compounds with magnesium orlithium.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples which are providedherein for purposes of illustration only and are not intended to belimiting unless otherwise specified.

EXAMPLES EXAMPLE 1 Synthesis ofN-dimethylsilyl-1,1,3,3,5,5-hexamethylcyclotrisilazane

Hexanes (50 ml) and HMCTS (0.031 mol, 6.76 g) were stirred at 0° C. forfive minutes in a 250 ml schlenk flask under argon. Dimethylchlorosilane(0.041 mol, 3.92 g) was added to the solution dropwise; the solutionturned slightly cloudy. After five minutes of stirring at 0° C.,n-butyllithium (10 ml of a 2.5M solution in hexane, 0.025 mol) was addedin small portions (1 ml) with a syringe. The solution turned cloudyafter the first addition. After all of the n-butyllithium had beenadded, a fine, white precipitate formed (lithium chloride). The solutionwas allowed to warm to room temperature and stirred overnight. Aftertransferring the mixture to a 250 ml roundbottom flask, the hexane wasremoved with a rotary evaporator. The vacuum source for the evaporatorwas a water aspirator and the bath temperature was 30° C. The resultingsolid/liquid mixture was distilled using a distillation apparatus inorder to isolate the liquid (pressure=1 torr; T=80° C.). The liquid wasthen vacuum distilled using a 20 cm column and vacuum jacketeddistillation head. The bath temperature did not exceed 100° C. and thepressure was 1 torr. Six fractions were collected and NMR spectra weretaken of each. In addition to starting material,mono-dimethylsilyl-substituted, di-dimethylsilylsubstituted, andtri-dimethylsilyl-substituted HMCTS compounds were identified.

EXAMPLE 2 Synthesis of 1,3-dichloro-1,1,3,3-tetramethylsilazane

With vigorous stirring, dimethyldichlorosilane (385.47 g, 2.99 mol) wasadded dropwise to a solution of HMCTS (202.93 g, 0.92 mol) in 800 ml oftetrahydrafuran (THF). The resultant slightly cloudy solution wasallowed to stir overnight. The following day, the THF was removed with arotary evaporator. The vacuum source was a water aspirator and the bathtemperature did not exceed 30° C. The liquid which remained was vacuumdistilled with a 38 cm column and vacuum jacketed distillation head. Thebath temperature did not exceed 65° C. and the pressure was less than 1torr. The title compound (179.78 g, 0.89 mol) was collected at 28°-31°C. under the above conditions. The yield was 60%.

EXAMPLE 3 Synthesis of 1,2,3-trichlorohexamethyltrisilazane

An ice-cold solution of 1,3-dichloro-1,1,3,3-tetramethylsilazane (10.08g, 0.05 mol) in hexane (100 ml) was prepared in a 250 ml schlenk flaskunder argon with stirring. N-butyllithium (16 ml of a 2.5M solution inhexane, 0.04 mol) was added dropwise with a syringe. After about fiveminutes of vigorous stirring, dimethyldichlorosilane (12.96 g, 0.10 mol)in hexane (50 ml) was added dropwise to the already cloudy solution. Thesolution was stirred for an additional five minutes before a smallamount of THF was added. After the dropwise addition of approximately 1ml of THF, a solid (LiCl) began to precipitate from the cloudy solution.One additional milliliter of THF was added in order to insure completereaction. The reaction was allowed to warm to room temperature and stirovernight. The solution was transferred to a 300 ml roundbottom flask.It was then placed on a rotary evaporator in order to remove the hexane,THF, and any remaining dimethyldichlorosilane. The resultingliquid/solid mixture was distilled with a distillation apparatus up to70° C. at a pressure of 1 torr. Over a period of one hour, the liquidcondensate crystallized to give approximately 10 g of a colorless solid.

EXAMPLE 4 Synthesis of 1,2,3-trichloropentamethyltrisilazane

An ice-cold solution of 1,3-dichloro-1,1,3,3-tetramethylsilazane (10.14g, 0.05 mol) in hexane (100 ml) was prepared in a 250 ml schlenk flaskunder argon with stirring. N-butyllithium (24 ml of a 2.5M solution inhexane, 0.06 mol) was added dropwise with a syringe. After about fiveminutes of vigorous stirring, methyldichlorosilane (11.87 g, 0.10 mol)in hexane (50 ml) was added dropwise to the already cloudy solution. Thereaction was allowed to warm to room temperature and stir for one hour.The solution was transferred to a 300 ml roundbottom flask. It was thenplaced on a rotary evaporator in order to remove the hexane and anyremaining methyldichlorosilane. The resulting liquid/solid mixture wasdistilled with a Kugelrohr distillation apparatus up to 80° C. at apressure of 1 torr. The colorless liquid was isolated in 78% yield(10.98 g).

EXAMPLE 5 Synthesis of (N-trimethylsilylamino)-ethyldichlorosilane,bis(N-trimethylsilylamino)etbylchlorosilane, andtris(N-trimethylsilylamino)ethylsilane

To a 2-liter round bottom flask was added ethyltrichlorosilane (1 mol,163.50 g) and HMDS (5 mol 806.95 g). The flask was equipped with athermometer, distillation column, distillation head with thermometer,condenser, vacuum distillation adapter, and collection flask. A dryingtube (calcium chloride) was attached to the outlet end of the vacuumdistillation adapter in order to trap water. The bottom temperature was127° C. which is the boiling point of HMDS. The top temperature(distillation head with thermometer) was 57° C. which is the boilingpoint of trimethylchlorosilane--a product of the desired reaction. Themixture was refluxed for two days; the temperatures were maintained atthe values indicated above. When no further trimethylchlorosilanedistilled over, the temperature was increased until the top temperaturewas also 127° C. The temperature was increased to insure that all of thetrimethylchlorosilane had distilled over. The final product mixturecontained the following compounds (by NMR): HMDS, trimethylchlorosilane,and the three title compounds.

EXAMPLE 6 Synthesis of N-lithio-hexamethyldisilazane

HMDS (440 ml, 340 g, 2.11 moles) was added to a 2-liter round bottomreaction vessel containing a magnetic stirring bar and fitted with areflux condenser. The top of the condenser was fitted to a vacuum/argoninlet with an exit port open to the atmosphere. The flask and condenserwere evacuated and then filled with argon. A slight flow of argon wasmaintained through the apparatus. N-butyllithium (800 ml of a 2.5 molarsolution, 2.0 moles) was then slowly added to the HMDS with vigorousstirring. The contents of the reaction flask were maintained at a gentlereflux. The bulk of the hexane and a portion of the excess HMDS werethen removed from the resulting yellow-brown solution by rotaryevaporation to leave a turbid, brownish liquid residue of the crudelithiated HMDS product. The reaction vessel was then flushed with argonand allowed to stand at ambient temperature for several hours, yieldinga mass of white crystals in a very turbid brown supernatant. Thesupernatant was poured off and the crystals washed twice with smallportions of chilled pentane. Volatiles were removed from the mass ofwhite crystals by rotary evaporation leaving a light brown liquidresidue of crude N-lithio-HMDS which froze to a solid mass on cooling.The product was purified by flash distillation (80-100° C., <0.01 torr)in a distillation apparatus equipped with a jacketed condenser bulb. Thedistillate collected as a clear colorless liquid which solidified to aclean white solid mass on cooling.

EXAMPLE 7 Synthesis of bis-(trimethylsilyl)-methylchlorosilylamine

A reaction flask was fitted with a reflux condenser and magnetic stirbar. The top of the condenser was fitted to a vacuum/argon inlet with anexit port open to the atmosphere. HMDS (440 ml, 340 g, 2.11 moles) wasthen added to the reaction flash and the flask and condenser wereevacuated and placed under an argon atmosphere. Butyllithium (800 ml ofa 2.5 molar solution, 2.0 moles) was then slowly added to the HMDS withvigorous stirring. The addition of butyllithium was adjusted to maintaina gentle reflux producing a brown turbid solution of lithiated HMDS. Thelithiated HMDS was then added to a reaction flask containing a mixtureof pentane (300 ml) and methyldichlorosilane (259 g, 2.25 moles) underargon. The lithiated HMDS was added at a rate slow enough to prevent anyboiling or refluxing. After a short time, a precipitate of white lithiumchloride formed. The reaction was then allowed to warm to ambienttemperature and allowed to stand for 20 hours. The white lithiumchloride settled to the bottom of the flask leaving a clearyellowish-brown supernatant. Solvents and excess dimethylchlorosilanewere then removed from the mixture by rotary evaporation and the productwas separated from the lithium chloride by flash distillation (50° C.,<0.1 torr). Flash evaporation yielded a clear colorless distillate whichwas further purified by fractional distillation to provide the titlecompound.

EXAMPLE 8 Synthesis of bis-(bis-trimethylsilylamino)-methylsilane

Dry N-lithio-hexamethyldisilazane (81 g, 0.50 moles) was transferred toa dry reaction flask under argon.Bis-(trimethylsilyl)-methylchlorosilylamine (144 g, 0.60 moles) was thenadded directly to the reaction flask under argon. The flask was thenfitted with a reflux condenser, purged with argon and maintained underan argon atmosphere. The temperature in the flask was then raised to110° C. and maintained at this temperature until all of the solids hadmelted. The mixture was swirled thoroughly to obtain a homogeneousmixture. The temperature of the reaction mixture was then incrementallyincreased to 170° C. over 3 hours in 20° C. increments. The reactionflask was held at 170° C. for 48 hours. The reaction mixture was thencooled and separated from lithium chloride which had formed by flashdistillation. The distillation yielded a clear distillate of the crudeproduct. This crude product was then purified by fractional distillationunder argon to yield the title compound.

EXAMPLE 9 Synthesis of Bis(dimethylamino)diethylsilane

A three-neck reaction flask was fitted with a stirring rod, an additionfunnel, and an argon gas inlet. Pentane (600 ml) were added to thereaction flask under an argon atmosphere and cooled to 0 ° C.Dimethylamine (338 g, 7.50 moles) was added to the reaction flask withstirring. Diethyldichlorosilane (196 g, 1.25 moles) was placed into theaddition funnel under argon and the diethyldichlorosilane was thenslowly added to the contents of the reaction flask with stirring. Awhite precipitate formed during addition of the diethyldichlorosilane.The contents of the flask were then extracted using a Soxhlet extractorand the pentane solvent was removed by rotary evaporation. The productwas purified by distillation.

EXAMPLE 10 Synthesis of Tris(dimethylamino)ethylsilane

Pentane (800 ml.) was added to a reaction flask analogous to the flaskof Example 9 and cooled to 0 ° C. Dimethylamine (347 g, 7.70 moles) wasadded to the reaction flask with stirring. Ethyltrichlorosilane (180 g.,1.10 moles) was then placed into the addition funnel under an argonatmosphere. The ethyltrichlorosilane was then slowly added to thecontents of the reaction flask with stirring. A white precipitate formedduring the course of this addition. The contents of the reaction flaskwere then extracted with an Soxhlet extractor and the pentane of theextract was removed by rotary evaporation to provide a clear, colorlesscrude product mixture. NMR spectra of this residue was consistent with amixture of tris(dimethylamino)ethylsilane andbis(dimethylamino)ethylchlorosilane.

A slurry of lithium dimethylamide was prepared by reacting 400 ml. of a2.5 molar solution of n-butyllithium in hexanes with a 20-30 % excess ofdimethylamine at 0° C. with vigorous stirring. The crude product mixturewas added to this slurry with vigorous stirring and the mixture was thenrefluxed with stirring for 3 hours. The bulk of the hexanes were removedby rotary evaporation and the product was removed from the lithium saltsby flash evaporation to dryness in a Kugelrohr distillation apparatusand then further purified by distillation.

EXAMPLE 11 Procedure for Deposition of Ceramic Coating

A quartz tube, ID 0.7 cm, was mounted in a 3 zone electric furnace andthe temperature raised to a desired temperature in an atmosphere offlowing nitrogen. At that temperature, a precursor was injected into thenitrogen flow at a point corresponding to the beginning of the hot zone.Precursor was delivered through a syringe needle and pumping system. Atypical flow rate was 1000 microliters per minute. The syringe tip waspositioned at the beginning of the isothermal zone. After treatment, thetemperature was dropped such that the cooled tube could be removed foranalysis at room temperature. The deposition was characterized bymeasuring the film thickness as a function of tube length and thusresidence time using Fourier Transform Infrared (FTIR) analysis. Theresults for ten different precursors are shown in Table 1.

                                      TABLE I                                     __________________________________________________________________________    Decomposition Characteristics of Chemical Precursors                                                                   FTIR                                                                          Peak                                                                      FTIR                                                                              Height                                                       Isothermal                                                                           Residence                                                                           Peak                                                                              (e.g.                                                        Temperature                                                                          Time  Time                                                                              Thickness                            Precursor                                                                           Chemical (IUPAC NAME)                                                                           (°C.)                                                                         (sec, cm)                                                                           (sec)                                                                             μm)                               __________________________________________________________________________    1     Bis(hexamethyidisilazane) or                                                                    800    5.0 @ 33                                                                            4.09                                                                              11                                         bis-(bis-trimethylsilylamino)-                                                methylsilane                                                            2     Dimethylaminotriethylsilane                                                                     800    0.5 @ 33                                                                            0.18                                                                              13                                                           750    5.0 @ 33                                                                            1.06                                                                              15                                   3     Diethylaminotriethylsilane                                                                      800    0.5 @ 33                                                                            0.22                                                                              11                                                           750    5.0 @ 33                                                                            1.44                                                                               9                                   4     1,1,3,3,5,5-Hexamethylcyclotrisilazane                                                          850    0.5 @ 33                                                                            1.0  2                                                           850    5.0 @ 33                                                                            6.0 14                                   5     Dimethylaminodimethylsilane                                                                     800    5.0 @ 33                                                                            2.95                                                                               3                                   6     Bis(dimethylamino)methylsilane                                                                  800    0.5 @ 33                                                                            0.14                                                                              11                                   7     Tris(dimethylamino)methylsilane                                                                 800    5.0 @ 33                                                                            1.44                                                                               8                                   8     Octamethyltrisilazane                                                                           860    0.4 @ 33                                                                            0.45                                                                               9                                                           800    5.0 @ 33                                                                            1.47                                                                              16                                   9     Bis(dimethylamino)diethylsilane                                                                 750    0.3 @ 33                                                                            0.60                                                                               4                                   10    Tris(dimethylamino)ethylsilane                                                                  750    0.5 @ 33                                                                            0.75                                                                              10                                   __________________________________________________________________________     Note: All injection concentrations = 400 μL/mol                            All carrier gas compositions = N.sub.2                                   

Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that, within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

What is claimed as new and desired to be secured by Letters Patent ofthe United States is:
 1. A compound having the structure ##STR7##wherein R₆ is hydrogen or C₁₋₂₀ alkyl, R₇ is hydrogen, Li or SiR₈ R₉ R₁₀where R₈, R₉, and R₁₀ are, independently, hydrogen or C₁₋₂₀ alkyl, andR₁₁ is hydrogen or C₁₋₂₀ alkyl; ora compound having the structure##STR8## wherein R₆ and R₁₂ are, independently, hydrogen or C₁₋₂₀ alkyl;or a compound having the structure ##STR9##
 2. A compound selected fromthe group consisting of heptamethyl-chloro-trisilazane,1,2,3-trichloro-hexamethyl trisilazane, ethyl-heptamethyl trisilazane,chloro-octamethyl trisilazane, N-lithio-1,3-dichloro-tetramethyldisilazane, 1,2,3-trichloro-hexamethyl trisilazane,1,1-dichloro-1-ethyl-trimethyl disilazane,N-dimethylsilyl-1,1,3,3,5,5-hexamethyl-cyclotrisilazane;bis(N-dimethylsilyl)-1,1,3,3,5,5-hexamethyl-cyclotrisilazane;tris(N-dimethylsilyl)-1,1,3,3,5,5-hexamethylcyclotrisilazane; andN-lithio-1,1,3,3,5,5-hexamethylcyclotrisilazane.
 3. The compound ofclaim 1, having the structure ##STR10## wherein R₆ and R₇ are as definedand R₁₁ is hydrogen or C₁₋₂₀ alkyl.
 4. The compound of claim 3, whereinR₆, R₇ and R₁₁ are C₁₋₈ alkyl.
 5. The compound of claim 1, having thestructure ##STR11## wherein R₆ and R₁₂ are, independently, hydrogen orC₁₋₂₀ alkyl.
 6. The compound of claim 5, wherein R₆ and R₁₂ are C₁₋₈alkyl.
 7. A volitile CVD precursor compound having the structure##STR12## wherein each R is, independently, hydrogen, C₂₋₂₀ alkyl, orNR₁ R₂ wherein R₁ and R₂ are, independently, C₁₋₂₀ alkyl, halogen orSiR₃ R₄ R₅ wherein R₃, R₄ and R₅ are hydrogen, C₁₋₂₀ alkyl or NR₁ R₂,and A is a divalent C₃₊ -alkylene arylene or alkylarylene group.
 8. Thecompound of claim 7, wherein R is C₂₋₈ alkyl, R₁ and R₂ are C₁₋₈ alkyland A is C₃₋₆ alkylene, C₆₋₁₀ arylene or C₇₋₁₆ alkylarylene.
 9. Thecompound having the structure ##STR13##
 10. The compound of claim 7,wherein each R is, independently, C₂₋₂₀ alkyl or NR₁ R₂.
 11. Thecompound of claim 8, wherein A is C₇₋₁₆ alkylarylene.
 12. The compoundof claim 8, wherein A is C₆₋₁₀ arylene.
 13. The compound of claim 7,wherein each R is hydrogen, C₂₋₈ alkyl or NR₁ R₂.
 14. The compound ofclaim 13, wherein one R is C₂₋₈ alkyl.